EP0046069A1 - Herbicidal and plant growth regulant diphenylpyridazinones - Google Patents

Herbicidal and plant growth regulant diphenylpyridazinones Download PDF

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Publication number
EP0046069A1
EP0046069A1 EP81303611A EP81303611A EP0046069A1 EP 0046069 A1 EP0046069 A1 EP 0046069A1 EP 81303611 A EP81303611 A EP 81303611A EP 81303611 A EP81303611 A EP 81303611A EP 0046069 A1 EP0046069 A1 EP 0046069A1
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Prior art keywords
alkyl
cyano
hydrogen
oxo
dihydro
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German (de)
English (en)
French (fr)
Inventor
William J. Pyne
John Lowbridge
In-Kook Chang
Florian Knotz
Larry J. Powers
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Diamond Shamrock Corp
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Diamond Shamrock Corp
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • A01N47/14—Di-thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/20—N-Aryl derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D237/14—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D237/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen

Definitions

  • This invention relates generally to diphenylpyridazinone derivatives which exhibit valuable herbicidal and plant growth regulant properties. This invention also relates to novel agricultural chemical compositions and methods for controlling, inhibiting and modifying the growth of a broad spectrum of plant life.
  • the class of compounds of the present invention has been found to be effective both in controlling unwanted plants as well as influencing the growth and development of valuable agricultural crops and aesthetic or ornamental plants.
  • Pharm., 41 (1973) 9-18 discloses selected N-2-substituted 5,6-diphenyl-3-oxo-4-cyano-2,3-dihydro- pyridazine species.
  • the article does not disclose any agricultural or like utilities.
  • selected diphenylpyridazinones of the present invention are disclosed in application U.S. Serial No. 11,416, filed February 12, 1979, now U.S. Patent No. 4,238,490, which compounds demonstrate pharmaceutical activity and, more particularly, are shown to be effective hypertensive agents.
  • active diphenylpyridazinones of the above general formula are formulated into novel compositions for selectively controlling and combating unwanted plant systems or for modifying the growth of various plant life.
  • the compounds of the present invention are various substituted diphenylpyridazinones of the general formula I below or the salts and the water hydrates thereof wherein
  • the compounds of the present invention have been found to be effective in controlling or inhibiting the growth of unwanted plants, e.g., broadleaf weeds and grasses.
  • the present invention contemplates methods for both preemergence control and postemergence control of undesired plants by applying to the plant, the plant situs or general growth environment, a herbicidally effective amount of an active diphenylpyridazinone compound of the invention, alone or in combination with a preselected carrier or adjuvant.
  • the compounds of the invention may be used to effect the growth of a desired plant.
  • plant growth regulant or “plant regulator” is defined as a substance which accelerates, retards, or otherwise alters the natural growth, development or maturation of plants.
  • observable plant growth regulant effects include, for example, yield enhancement, root or top growth stimulation or inhibition, tolerance to temperature extremes, nonphytotoxic herbicide-like responses and the like.
  • the compounds of the present invention have been found to be effective for regulating or modifying the growth of a wide variety of plant life including, ornamental plants; turf grasses, cotton, soybeans and tobacco.
  • the herbicidally-active diphenylpyridazinones of this invention generally will be applied at between about 0.03 kg/heetare to about 8.00 kg/hectare; preferably, 0.25 kg/hectare to 4.00 kg/hectare and, most preferably, 0.5 kg/hectare to 2.00 kg/hectare.
  • the desired plant growth regulant effects are obtained at application rates of between about 0.01 kg/hectare to 8.00 kg/hectare, preferably, 0.125 kg/hectare to 2.00 kg/hectare and, most preferably, 0.25 kg/hectare to 2.00 kg/hectare.
  • Exemplary of preferred compounds for use in the compositions and methods of the present invention are compounds of the above general formula I wherein
  • Ethanol 2-(5-cyano-1,6-dihydro-6-oxo-3,4-diphenylpyridazin-l-yl); Acetic Acid, 5-cyano-1,6-dihydro-6-oxo-3,4-diphenylpyridazin-l-yl; Acetic Acid, 5-cyano-1,6-dihydro-6-oxo-3,4-diphenylpyridazin-l-yl ethyl ester; Propionic Acid, 3-(5-cyano-1,6-dihydro-6roxo-3,4-diphenylpyridazin-1-yl); Propionic Acid, 3-(5-cyano-1,6-dihydro-6-oxo-3,4-diphenylpyridazin-1-yl)ethyl ester; Propionic Acid, 3-(5-cyano-1,6-dihydro-6-oxo-3,4-diphenylpyridazin-1
  • Acetic Acid 5-cyano-l,6-dihydro-6-oxo-3,4-diphenylpyridazin-1-yl
  • Acetic Acid 5-cyano-l,6-dihydro-6-oxo-3,4-diphenyl- pyridazin-1-yl ethyl ester
  • Propionic Acid 3-(5-cyano-l,6-dihydro-6-oxo-3,4-diphenylpyridazin-1-yl)
  • Propionic Acid 3-(5-cyano-l,6-dihydro-6-oxo-3,4-diphenylpyridazin-1-yl)ethyl ester
  • Propionic Acid 3-(5-cyano-1,6-dihydro-6-oxo-3,4-diphenylpyridazin-l)-l-propyl ester
  • Propionic Acid 3-(5-cyano-1,6-dihydro-6-oxo-3
  • alkyl represents 1 to 8 carbon atoms, unless otherwise specified and includes all straight chain and branch chain moieties
  • alkenyl and alkynyl represent 2 to 6 carbon atoms unless otherwise specified and includes all straight chain and branch chain moieties
  • salts includes alkali metal salts, alkaline earth metal salts, acid addition salts, quaternary ammonium salts and amino acid salts.
  • the diphenylpyridazinones of the present invention may be prepared by several alternative acceptable methods. However, all the compounds of this invention can be derived ultimately from Compound IV or Compound V below which compounds can be prepared according to the general reaction scheme set out below.
  • the benzil (II) starting material below can be purchased commercially or prepared from the desired benzaldehyde compound by any well known or conventional technique.
  • Other compounds of this invention can then be derived by, for example, treating IV with a halogenated alcohol or by treating V with ethylene carbonate to obtain the hydroxyalkyl derivatives.
  • the hydroxyalkyl derivatives can further be used to prepare, for example, the various ester derivatives by treatment with the requisite anhydride; or the various carbamate derivatives can be prepared from the hydroxyalkyl derivative by treatment with the requisite isocyanate.
  • the various ester derivatives can be further hydrolyzed to the corresponding acid derivatives or used in preparing the amino acid ester derivatives of this invention.
  • the desired diphenylpyridazinone derivative can be obtained by appropriate selection of the particular alkyl, alkoxy, alkoxycarbonyl, hydroxyalkyl, alkenyl, and the like reactant.
  • a few of the foregoing preparative procedures are set out in Knotz, Sci. Pharm., 41, (1973) pp. 9-18.
  • the specific reaetants, procedures and conditions are further to be illustrated in the examples that follow this discussion.
  • the active compounds according to the instant invention may be utilized, if desired or necessary, in the form of acceptable formulations or compositions containing liquid or solid inert pesticidal carriers or adjuvants in addition to the active agent(s) to provide solutions, emulsions, suspensions, dusts, wettable powders, etc., which facilitate the use and application of the compounds of the invention to preselected substrates.
  • compositions and formulations may be prepared in a known manner, for instance, by admixing the active compounds of the invention with dispersible liquid diluents and carriers optionally in combination with other vehicles, such as surface-active agents, including emulsifying agents or dispersing agents and suitable solubilizing or diluting solvents as described in the above-mentioned U.S. Patent Nos. 3,960,542 or 4,050,921.
  • aromatic hydrocarbons e.g., benzene, toluene, xylene, etc.
  • halogenated aromatic hydrocarbons e.g., chlorobenzenes
  • paraffins e.g., petroleum fractions
  • chlorinated aliphatic hydrocarbons e.g., methylene chloride, etc.
  • alcohols e.g., methanol, ethanol, propanol, butanol, etc.
  • ethers and ether alcohols e.g., glycol monomethyl ether, etc.
  • amines e.g., ethanolamine, etc.
  • amides e.g., dimethylformamide, etc.
  • ketones e.g., acetone, etc.
  • solid inert carriers such as kaolins, alumina, silica, calcium carbonate, talc or kieselguhr may be employed.
  • Appropriate nonionic and anionic emulsifying agents or surface active agents, such as polyethylene oxide esters of fatty acids and fatty alcohols, alkyl sulfonates and aryl sulfonates may be used in conjunction with the aforesaid carriers, vehicles, adjuvants and solvents.
  • compositions in accordance with the present invention may also contain other compatible growth regulants, fungicides, nematocides, insecticides, fertilizers and other known herbicides. According to the accepted practices in the formulating art, when combined with other active agents or with carriers, vehicles and the like, the compositions of the invention contain from about 0.01 percent to about 99 percent, by weight, of the instant compounds as the active components thereof.
  • compositions of the invention may be applied, for example, by spraying, atomizing, dusting, soil injection, seed pretreatment, etc., to obtain the desired herbicidal and plant growth regulant responses.
  • Examples 1 through 6A illustrate the reactant compound precursors from which the pyridazinone derivatives were synthesized. These compound predecessors are summarized in Table I and may be synthesized in situ or may in some cases be purchased commercially.
  • a one liter monel metal bomb was charged with 40 g (0.136 mole) of the product of Example 2 and 9.5 mls of distilled water.
  • the bomb was sealed and chilled in dry ice and acetone bath.
  • the system was evacuated with a vacuum pump.
  • About 190 grams (2.0 mole) of sulfur tetrafluoride gas was injected into the bomb and sealed.
  • the bomb was placed on a rocker apparatus, allowed to warm to room temperature, then heated to 50° C and agitated overnight.
  • the bomb was allowed to cool, vented and scrubbed with Nitrogen before opening.
  • the solvent was distilled at reduced pressure and the residual material poured down a silica column.
  • Examples 7 through 17 illustrate hydroxyalkyl derivatives of diphenylpyridazinones. These compounds are summarized in Table II. Those compounds shown in Table II that are not shown by specific preparatory example have been synthesized in accordance with one of the examples manifested below.
  • the necessary benzil starting material is not commercially available, it may be prepared from the desired benzoin which in turn can be synthesized from the corresponding aldehyde and potassium cyanide.
  • the benzil is caused to react with the cyanoacetohydrazide in DMF to give the benzilmono- acetohydrazide.
  • the latter compound is reacted with 8% sodium hydroxide to give the corresponding diphenylpyridazinone sodium salt. This salt can then be reacted with hydrochloric acid to give the corresponding -NH compound.
  • the 5,6-diphenyl-4-cyano-2-hydroxymethyl-3-(2H)-pyridazinone also reverted back to the original starting material when recrystallized from ethyl alcohol.
  • the infrared spectrum of the recrystallized solid and the original starting material were superimposable.
  • Examples 18 through 29 illustrate various ester derivatives of diphenylpyridazinones. These compounds are summarized in Table III.
  • Acetate ester of 2-(2'-hydroxyethyl)-4-cyano-5,6-diphenyl-3-(2H)-pyridazinone 10 grams (0.031 mole) of 2-(2'-hydroxyethyl)-4-cyano-5,6-diphenyl-3-(2H)-pyridazinone was reacted with excess acetic anhydride. This mixture was heated to 100° C, at which temperature all the solid dissolved. The solution was heated an additional hour, cooled, poured into excess water and the precipitant solid was filtered, washed with water and finally petroleum ether. This material was recrystallized from ethyl alcohol to give 6.0 grams of a solid which melted at 120° C. The infrared spectrum showed the nitrile band at 4.5 ⁇ ; 2 carbonyl groups, one at 5.7 ⁇ and the other at 6.0 ⁇ .
  • Examples 30 through 63 illustrate acetate ester derivatives of diphenylpyridazinones. These compounds are summarized in Table IV and portions of Table XXVIII.
  • the solvent was distilled at reduced pressure and the residual oil purified by passing it through a dry column and diluting it with 90% chloroform and 10% ethyl acetate. There was isolated 1.2 grams of the desired product. An analytical sample was prepared by recrystallizing a small sample of this product from ethyl alcohol.
  • Example 30 54.6 grams of the product of Example 30 was heated to reflux with aqueous methyl alcohol (40% water and 60% methyl alcohol). This solution was refluxed for 5 hours, cooled and the solvent distilled at reduced pressure. The residual solid was taken up in benzene, filtered, cooled, and the precipitant product was filtered, washed with petroleum ether and air dried. This solid was recrystallized form absolute ethyl alcohol to give 17.8 grams of a white solid that melted at 117-119° C. The infrared spectrum showed the NH band at 3.1) 1 , and two carbonyl bands.
  • Examples 64 through 85 illustrate propionate ester derivatives of diphenylpyridazinones. These compounds are summarized in Table V and portions of Table XXVIII.
  • Example 64 The synthesis of the product of Example 64 is performed in accordance with that procedure set forth in Example 31.
  • Example 65 The synthesis of the product of Example 65 is performed in accordance with that procedure set forth in Example 32.
  • Example 3 3.3 grams (0.01 mole) of the product of Example 3 was caused to react with 1.1 grams (0.01 mole) of ethyl acrylate in 30 mls of pyridine containing 1.5 mls of distilled water. This solution was heated to reflux for 8 hours, cooled and the solvent distilled at reduced pressure. The residual solid was taken up in ethyl acetate, washed with water and separated. The organic layer was dried over sodium sulfate, filtered and the solvent distilled at reduced pressure. The residual solid was recrystallized from 95% ethyl alcohol to give 0.7 gram of a solid melting at 81-83° C. The infrared spectrum showed the nitrile band at 4.5 ⁇ , two carbonyl bands, one at 5.8 ⁇ , the other at 6.1 u.
  • Examples 86 through 112 illustrate ester and acid derivatives of diphenylpyridazinones. These compounds are summarized in Table VI.
  • Pentanoic acid 2-(5-cvano-1,6-dihvdro-6-oxo-3,4-diphenylpyridazin-1-yl) ethyl ester
  • Example 87 is performed in accordance with that procedure set forth in Example 30.
  • the solvent was distilled at reduced pressure and the residual solid was taken up in ethyl acetate, washed with water, separated and the organic layer dried over Na 2 SO 4 .
  • the solvent was distilled at reduced pressure and the crude product recrystallized from absolute ethyl alcohol to give 2.6 grams (30.6%) yield of the desired product.
  • Example 89 is performed in accordance with that procedure set forth in Example 31.
  • Example 90 5.0 grams (0.012 mole) of the product of Example 90 was reacted with 7.5 grams (0.0877 mole) of anhydrous sodium acetate and 5.0 grams (0.071 mole) of hydroxylamine hydrochloride in 100 mls of aqueous ethyl alcohol. This mixture was heated on a hot water bath for one hour. The solvent was removed at reduced pressure by employing a rotovap and the residual liquid poured into excess hydrochloric acid and the precipitant yellow solid was filtered, washed with water and air dried. This solid was recrystallized from absolute ethyl alcohol to give 1.5 grams of a white solid melting at 162-166° C. The infrared spectrum showed the nitrile band at 4.5 ⁇ , and two carbonyl bands, one at 5.7 ⁇ , the other at 6.0 u.
  • Examples 113 through 134 illustrate various salt derivatives of diphenylpyridazinones. These compounds are summarized in Table VII.
  • Examples 135 through 147 illustrate amide derivatives of diphenylpyridazinones. These compounds are summarized in Table VIII.
  • Example 136 is performed in accordance with that procedure set forth in Example 32.
  • Examples 148 through 157 illustrate carbamate derivatives of diphenylpyridazinones. These compounds are summarized in Table IX.
  • Example 71 6.6 grams (0.016 mole) of the product of Example 71 was reacted with 2.02 grams (0.016 mole) of phenyl isocyanate in 60 mls of dry toluene. This solution was heated on a steam bath for 1 hour. The precipitant was filtered, washed with petroleum ether and air dried. There was isolated 8.6 grams (100%) yield of a yellow solid that melted at 154-155° C. The infrared spectrum showed the NH band at 3.1, the nitrile band at 4.5 ⁇ , and two carbonyl bands, one at 5.8 ⁇ , the other at 6.1 ⁇ .
  • Examples 158 through 173 illustrate selected cyclic amino, dithiocarbamate, ether, mercapto, nitrate and sulfonyl derivatives of diphenylpyridazinones. These compounds are summarized in Table X.
  • Example 158 is performed in accordance with that procedure set forth in Example 9. The appropriate chloroester was used in Example 158 rather than the chloroalcohols used in Example 9.
  • the salt (1) was prepared from the reaction of 2.13 grams (0.021 mole) of Cis-2,5-dimethylpyrrolidine 99% Cis isomer and 5.9 grams of the product of Example 1 in 100 mls of aqueous ethyl alcohol. Into this solution was added 4.0 grams of 40% aqueous formaldehyde. This mixture was heated on a steam bath for 20 minutes. The excess solvent was distilled at reduced pressure and the residual yellow solid was recrystallized from absolute ethyl alcohol to give 4.0 grams (57.8%) of a solid that melted at 156" C.
  • Example 2 8.0 grams (0.0175 mole) of the product of Example 1 was reacted with 2.1 grams of ethyl-vinyl sulfone in 60 mls of pyridine. This solution was heated on a steam bath for 2 hours, cooled and the solvent distilled at reduced pressure. The residual oil was taken up in ethyl alcohol. 5.0 grams (72% yield) of a solid precipitated and was filtered, washed with petroleum ether and air dried. The infrared spectrum showed the nitrile band at 4.5 ⁇ , the carbonyl band at 6.0 ⁇ , the S0 2 band at 8.7 ⁇ .
  • Example 2 4.0 grams (0.014 mole) of the product of Example 1 was reacted with 2.37 grams (0.014 mole) of 2-nitrobutyl acetate in 100 mls of dry pyridine. This solution was heated to reflux for 1 hour, cooled and the solvent distilled at reduced pressure. The residual solid was recrystallized from methyl alcohol to give 2.0 grams (37% yield) of a white-yellow solid melting at 154-155° C. The infrared spectrum showed the C-C band at 3.5 ⁇ , the nitrile band at 4.5 u, and the amide carbonyl band at 6.0 ⁇ .
  • Example 174 through 190 illustrate amino acid derivatives of diphenylpyridazinones. These compounds are summarized in Table XI.
  • the residual solid was taken up in ethyl acetate.
  • the ethyl acetate solution was washed first with 0.5 molar hydrochloric acid followed with 0.5 molar sodium bicarbonate and finally with brine.
  • the solution was dried over MgSO 4 , filtered and the solvent distilled at reduced pressure.
  • the crude product was recrystallized from a mixture of ethylacetate and petroleum ether to give 11 grams (66% yield) of the desired product that melted with decomposition at 114-115° C.
  • Example 174 5.2 grams (0.0124 mole) of the product typified in Example 174 was dissolved in a mixture of 25% aqueous acetone at 0° C. 12.5 mls of 1 molar sodium hydroxide (0.5 grams, 0.0125 mole) was added to this solution and the mixture stirred for 2 hours at 0° C. The acetone water solvent was distilled at reduced pressure and the residual mixture extracted with chloroform. The organic layer was then separated and extracted with 1M sodium bicarbonate (20 mls). The aqueous fractions were combined and made acid to Congo Red (1 molar HC1). The solid that separated out was extracted with 200 mls of chloroform, and then with 3 further aliquots (100 mls).
  • This phthaloylamino derivative (33.45 g, 75 mmole) was dissolved in 500 ml of boiling methanol. The slightly cooled solution was treated with 10.3 ml of 85% hydrazine hydrate and heated under a steam bath reflux for 2 hours. The reaction mixture was cooled to room temperature, and evaporated in vacuo. The orange semi-solid residue was digested with 250 ml of 50% aqueous acetic acid.
  • reaction mixture was stirred for 2 hours, maintaining the ice bath, and treated with a solution of 2-(2-aminoethyl)-4-cyano-5,6-diphenyl-(2H)-pyridazin-3-one in dimethylformamide, prepared as follows: the hydrobromide (7.94 g, 20 mmole) was partitioned between 1M sodium hydroxide (22 ml) and chloroform (50 ml). The organic phase was separated and the aqueous phase extracted twice with chloroform aliquot. The chloroform extract was washed with brine, dried and evaporated to an orange semi-solid residue which was taken up in dimethylformamide.
  • reaction mixture was stirred overnight at room temperature. Approximately 4.5 g of dicyclohexylurea was filtered, and the filtrate evaporated in vacuo to a viscous oil which was taken up in 100 ml of ethyl acetate containing 3 drops of 50% aqueous acetic acid.
  • the solution was set aside for 1 hour at toom temperature, filtered, and washed 3 times each with 0.5M HC1, 5% NaHC0 3 , and brine, dried, and evaporated in vacuo to a viscous oil which was crystallized by dissolution in ethyl acetate, dilution with ether and the careful addition of hexane to yield 5.2 g (60%) of the pyridazinone derivative.
  • a solution of pivaloyl chloride in 1 ml of 3M acetonitrile was added in dropwise manner with stirring to a precooled (0 to -5° C, ice-salt bath) solution of 1.04 grams of the product of Example 64 and 0.46 ml of triethylamine in 10 ml of acetonitrile.
  • Examples 223-229 illustrate various hydrazine derivatives of diphenylpyridazinones. These compounds were prepared in 48% to 100% yields from the reaction of the appropriate hydrazide and the desired phenyl isothiocyanate or alkyl isocyanate in 95% ethanol. The compounds are summarized in Table XXIX.
  • test formulations of representative compounds are prepared by mixing 20 ml of an acetone solution containing 0.0416 g of the test compound with 20 ml of water containing 0.02 ml of Ortho X-77 surfactant.
  • the resultant formulations contain 1040 ppm of test compound, 50 percent, by volume, of acetone and 0.05 percent, by volume, of surfactant. Appropriate lower concentrations are obtained by diluting this formulation with surfactant-acetone solution so that the concentration of adjuvants is maintained at the original levels.
  • Seeds of three broadleaf, three grassy weed species and three crop species are planted in the soil contained in 10 x 8 x 3 inch fiber pans filled with 2.0 inches of pasteurized soil (Kingsville sandy loam).
  • the broadleaf species are pigweed (Amaranthus retroflexus L.), velvet leaf (Abutilon theophrasti Medic.) and mustard (Brassica kaber (DC.) Wheeler); the grasses are red millet (Panicum milliaceum L.), green foxtail (Setaria viridis (L.) Beauv.) and barnyard grass (Echinochloa crus-galli (L.) Beauv.), and the crops are cotton (Gossvpium hirsutum L.
  • pans are then sprayed so that the soil surface is uniformly covered with dilutions of the stock formulation providing dosage rates of the test compounds corresponding to 8, 4, 2, 1, 0.5, 0.25, 0.12, 0.06, etc., kg/hectare. Two weeks after treatment, percent control (plant kill) at each dosage rate is estimated.
  • the postemergent herbicide tests are carried out in the same manner described above, except that the herbicide formulations are applied to the foliage of the seedling plants.
  • the compounds of the invention were also evaluated relative to plant growth regulant activity against three plant species in a petri dish test.
  • the test is divided into a primary test where 500 ⁇ g and 100 ⁇ g chemical per petri dish (100 x 25 mm, disposable) are tested simultaneously and a secondary test where 50 ⁇ g to 0. ⁇ g chemical per petri dish are tested simultaneously. Compounds which pass the primary test are further evaluated in the secondary test.
  • a special petri dish test may also be run to evaluate particular test compounds, in which case the primary tests and secondary tests are conducted simultaneously.
  • three plant species are planted in a petri dish which has been treated with the test substance.
  • the three species are as follows: 1) a mixture of approximately 50 percent light-sensitive and 50 percent light-insensitive lettuce (Lactuca sativa L. 'Grand Rapids'); 2) soft red winter wheat [Tritieum aestivum L. (Aestivicum Group) 'Abe']; and 3) pasture- type perennial ryegrass (Lolium perenne L. 'Linn').
  • Wheat and perennial ryegrass seeds are surface-sterilized with 1 percent sodium hypochlorite for 10 minutes and 5 minutes, respectively. - I
  • test compound is formulated in acetone and aliquots of the test formulation are placed on three layers of sterilized filter papers (Whatman No. 1, 8.26 cm diameter) in each petri dish. As soon as the acetone evaporates, 7 ml of deionized water are added into each petri dish with an appropriate automatic dispenser. Then, 5 to 8 wheat seeds, 10 to 15 perennial ryegrass seeds and 10 to 15 lettuce seeds are placed on the filter paper of each petri dish. Dishes are then covered and seeds are germinated for 3 days at 20°C at a relative humidity of 65% in the dark. The dishes are then removed from the dark growth chamber and maintained in lighted environmental growth chambers for 4 days.
  • Test solutions were either applied into the soil as a drench or sprayed onto the plant foliage one month after planting. At this time, cotton plants were in the 1-2 true leaf stage. Treatment volume was 5 mls which is equivalent to a 500 gal/A field rate when based on pot area. In the case of foliar spray treatments, which were applied with a cone-type nozzle at 12 psi, treatment volume was sufficient to wet all foliage without runoff. During the foliar spray treatments, a plexiglass shield covered the soil. Foliar treated plants were bottom watered subsequent to treatment to prevent chemical runoff.
  • Test solutions were prepared by dissolving 24 mg of chemical or acid equivalent, in the case of salt formulations, in 17.5 mls of acetone and diluting to 50 mls with water. Five mls (480 ppm) of this solution per pot was calculated to be equivalent to a 2 kg/ha rate when based on pot area. Appropriate dilutions were made with a 35% acetone solution to attain 1, 1/2, 1/4 and 1/8 kg/ha rates. One half ml of 0.5% Triton X-155 (Triton X-155 and Triton X-114, as appearing herein, are alkylaryl polyether alcohol surfactants obtainable from Rohm & Haas Company) was added to each 5 mls of test solution. Control plants were either foliar sprayed or soil drenched with 35% acetone and .05% Triton X-155. All treatments were replicated twice.
  • Triton X-155 Triton X-155 and Triton
  • Plant height was evaluated by measuring the distance from the soil surface to the plant apex at 0 and 3 weeks after treatment for foliar sprayed cotton, and at 0 and 5 weeks after treatment for soil treated cotton.
  • Selected compounds of the present invention were tested for chemically controlling vegetative growth of cotton subsequent to a defoliation treatment. Regrowth is undesirable because it decreases mechanical harvesting efficiency, lowers fiber quality by adding a green stain to cotton fibers and/or providing moisture which can cause fiber deterioration during the preginning stage.
  • Example 132 was formulated by dissolving the required amount of compound in 10.5 mls of acetone and diluting to 30 mls with water to attain the appropriate test rates.
  • the compound of Example 64 was formulated as a 10% flowable (w/w) and diluted to 30 mls with a 1% base formulation minus active ingredient to attain the appropriate test rates. Regrowth was evaluated by the method described previously one month after treatment.
  • test solutions were applied as a foliar spray treatment with an air brush at 12 psi 12 days after defoliation. At this time mature cotton leaves had abscissed and new leaves (regrowth) were beginning to emerge.
  • the compound of Example 31 was formulated as a 2 EC and diluted with water to attain appropriate rates.
  • An appropriate amount of the compound of Example No. 124 was weighed and diluted to 9 mls with water and 1 ml of 10% Triton X-114 was added. Treatment volume was 10 mls which is equivalent to a 57 gal/A rate. Regrowth was evaluated by the method previously described one month after treatment.
  • the compounds of the present invention were evaluated for producing ornamental plants which are more aesthetically satisfying to consumers.
  • Test solutions were prepared by dissolving 18 mg of chemical in 50 mls of acetone and diluting to 100 mls with water. Ten mls (180 ppm) of this solution per pot was calculated to be equivalent to 1 kg/ha when based on pot area. Appropriate dilutions were made with a 50% acetone solution to attain 0.5 and 0.25 kg/ha rates. One half ml of 0.5% Triton X-155 was added to each 10 mls of test solution.
  • A-Rest a commercial standard by Eli Lily was prepared by diluting 6.8 mls of the product to 10 mls with a 50% acetone to attain a 1 kg/ha rate. Appropriate dilutions were made with a 50% acetone solution to attain 0.5 and 0.25 kg/ha rates. Test solutions were sprayed onto plants with a cone-type nozzle air gun at 15-20 psi. All 'treatments were replicated twice. Control plants were sprayed with 10 mls of 50% acetone. Plant height was evaluated 8 weeks after treatment by measuring the distance between the soil level and the top of the plants.
  • the invention compounds were evaluated for ability to reduce algal population in recreational and other waters.
  • Chlamydomonas reinhardi [wt. (+)] were grown in synehromonous culture using a basal salt medium supplemented with acetate at pH 7.2. Cells grown to approximately 2 x 10 6 per ml were diluted to 2.5 x 10 5 cells per ml with algal growth media. Ten mls of algal culture was dispensed into 25 ml Erlenmeyer flasks. Test solutions were prepared by solubilizing a weighed amount of test compound in 10 mls of dimethylsulfoxide (DMSO) to yield a 10 -2 M concentration. Appropriate dilutions were made with DMSO to attain decreasing chemical concentrations.
  • DMSO dimethylsulfoxide
  • test solution was added to each flask.
  • Control flasks received 0.1 ml of DMSO. Flasks were plugged with cotton and all procedures were performed under sterile conditions. All treatments were replicated twice.
  • Algal cultures were allowed to incubate in the presence of the chemical for 2.5 days in a water bath-shaker at 25° C under a 12 hr. light/12 hr. dark cycle. At the end of the incubation period, the algal growth was terminated by adding 0.5 mls of 50% w/v gluteraldehyde to each test flask. The number of algal cells per ml of culture in treated'vs. control flasks was determined by replicate counting with a hemacytometer.
  • the diphenylpyridazinones of the present invention have been found to be effective in regulating the growth of leguminous plants, especially soybean.
  • the growth regulatory effects which can be observed are: height reduction, inhibition of terminal and axillary bud growth, reduced leaf size, curled leaves and dark green-colored leaves.
  • Soybean plants especially indeterminate types of soybeans, produce unnecessary vegetative growth during the reproductive growth stage of development.
  • the unnecessary vegetative growth includes terminal bud growth and branching during the reproductive growth stages. This growth does not contribute to the yield, but reduces the yield of soybean.
  • By inhibiting such unnecessary vegetative growth more photosynthates and nutrients can be translocated to yield components such as the pod, thus improving the "harvest index" of the soybean.
  • Such growth inhibition can also improve water economy of soybean plants and prevent senescence during reproductive stages, leading to a yield increase.
  • Diphenylpyridazinones of the present invention have demonstrated high sucker control activity in greenhouse tests.
  • the compounds of Example Nos. 30, 31, 124, 64, 120, 113 and 67 were selected, on the basis of the results of the primary plant growth regulant screen, to treat greenhouse-grown burley or flue-cured tobacco plants.
  • each compound contained 0.05 to 0.2% Triton X-114 or 0.025% Triton X-155.
  • Commercial varieties of burley or flue-cured tobacco were grown in a greenhouse at a final size of 1/4 to 1/2 of the field-grown plants.
  • Five to 20 ml of test formulations were sprayed on the center of each topped plant or drenched into soil of each pot containing a topped plant at button, early flower or late flower stage.
  • Control of the top 5 suckers were evaluated 21 to 42 days after treatment and % control was calculated by the formula: where TNS is the fresh weight of suckers of the topped check and TR is the fresh weight of suckers of the treated plants.
  • the top 5 suckers have the greatest potential to regrow after topping of flower bud or flowers.
  • Flue-cured tobacco plants were grown in the greenhouse until maturity. Two plants were topped at the button stage (a tobacco developmental stage showing flower bud formation) and grown for 6-8 days until the top-most leaf span reached 6-8 inches and the top-most sucker growth reached 1-3 inches. The plants at this stage are very similar to field-grown plants in the early flower stage. If the plants at the button stage are not topped but grown further in the greenhouse, they will reach the early flower stage in 6-8 days. These plants are referred to as early topped early flower stage plants. Another two plants at the button stage of tobacco development were topped before chemical application.
  • the selected pyridazinone compounds were formulated as a 6% EC (emulsifiable concentrate).
  • One early topped early flower stage plant and one button stage plant were sprayed with each compound at 1.5 mg or 3 mg per plant, except the compound of Example 38 (sprayed at 3 mg or 6 mg per plant).
  • Each compound to be tested was formulated into a 10 ml emulsified solution with a constant surfactant concentration for both rates of application.
  • the test formulations were sparyed with a Hudson Hydragun ®on the center of each plant. The nozzle of the Hydragun was adjusted to generate a coarse spray.
  • Sucker control was evaluated 5 weeks after treatment. Suckers from the top 5 nodes were counted and fresh weights of the sucker from the control (topped check) and the treated were determined. Also malformation of top 3 leaves of plants sprayed at the button stage was evaluated as follows: % sucker control was calculated as follows: (This formula defined on page 113.)
  • diphenylpyridazinones of the present invention can be useful for controlling the growth an morphology of woody perennial plant species.
  • these agents may act to chemically prune woody ornamental species.
  • these pyridazinones may effectively control the growth of brush in right- of-way applications.
  • Testing was performed to provide information concerning the effects of selected diphenylpyridazinones on woody perennial growth.
  • a tree and a shrub species were selected along with two diphenylpyridazinone acids for greehouse experimental models.
  • the compounds of the present invention demonstrate excellent herbicidal activity and broad spectrum plant growth regulant activity at relatively low application rates.
  • the compounds of the present invention can have plant growth regulant utility in numerous other areas among which there may be especially mentioned stimulation of cotton boll opening for yield enhancement and harvest efficiency improvement, tree growth retardation for reduced pruning and reduction of maintenance, sugar cane growth regulation for increased sugar content, control of bud-breaking in fruit trees for reduced damage from frost, sprout control for onions, potatoes and other stored vegetables to improve quality, growth regulation of corn and small grains for yield enhancement and growth regulation of the potato plant for yield enhancement.
  • compounds of the invention can find use for sugar beet bolting control to increase the sugar beet yield as well as the sugar content; and, in addition, to control the weed beet plant. Similar to the concept for tobacco sucker control, control of the sugar beet flower bud can increase the size of the sugar beet root and the sugar content in the root. Also by controlling flower and seed head formation, control of weed beets, which is a severe problem in current sugar beet production in Europe, can be accomplished during the next growing season.
  • banana sucker control to increase yield of the mother plant and to speed up growth of a daughter plant
  • tree and hedge growth retardation and brush control for industrial areas and under powerlines
  • growth retardation of cover crops in orchards, no-till farmlands and soil conservation yield enhancement for such crops as a) alfalfa - increase in branching, b) small grains - reduced stature and reduced lodging, c) sugarcane - inhibition of flowering, d) peanut - inhibition of unnecessary vegetative growth, and e) sunflower - reduced stature and reduced lodging
  • male- sterilant or gametocyte for hybrid seed production
  • tree sucker control chemical flower and fruit thinning
  • vine control for grapes inhibition of rhizomes
  • control of seed germination are also be found in the biologist

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
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  • Plural Heterocyclic Compounds (AREA)
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  • Hydrogenated Pyridines (AREA)
EP81303611A 1980-08-07 1981-08-06 Herbicidal and plant growth regulant diphenylpyridazinones Withdrawn EP0046069A1 (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5883090A (en) * 1995-10-09 1999-03-16 Merck Patent Gesellschaft Mit Beschrankter Haftung Endothelin receptor antagonists
WO2000050408A1 (fr) * 1999-02-26 2000-08-31 Kowa Co., Ltd. Derives de pyridazin-3-one et medicaments contenant ces derives
US10899743B2 (en) 2015-08-05 2021-01-26 Bristol-Myers Squibb Company Substituted glycine derived FXIA inhibitors

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IL112014A (en) * 1993-12-24 1999-10-28 Rhone Poulenc Agrochimie 1,3-Oxazin-4-one derivatives and herbicides containing the same
PL194175B1 (pl) * 1997-08-22 2007-05-31 Abbott Lab Pirydazynony, zawierające je kompozycje farmaceutyczne oraz ich zastosowanie
ATE302759T1 (de) * 1998-10-27 2005-09-15 Abbott Lab Prostaglandin endoperoxyde h synthase biosynthese inhibitoren
ES2544869B2 (es) * 2014-03-04 2016-01-18 Universidade De Vigo Derivados de piridazin-3(2H)-ona inhibidores selectivos de la isoforma B de la monoaminooxidasa
IL295336A (en) 2020-02-14 2022-10-01 Fmc Corp -Diphenyl-3(2h)pyridazinones are converted for use as fungicides

Citations (3)

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Publication number Priority date Publication date Assignee Title
BE528490A (enrdf_load_stackoverflow) *
BE531615A (enrdf_load_stackoverflow) *
EP0018063A1 (en) * 1979-02-12 1980-10-29 Diamond Shamrock Corporation Pyridazin (2H)-3-ones, process for their preparation and their use in antihypertensive agents

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DD19629A (enrdf_load_stackoverflow) *
DE2233937A1 (de) * 1972-07-11 1974-01-31 Basf Ag Arylmercapto-naphtholactame
US4013658A (en) * 1975-07-03 1977-03-22 Eli Lilly And Company Synthesis of 3,5-diphenyl-4(1h)-pyridazinones

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
BE528490A (enrdf_load_stackoverflow) *
BE531615A (enrdf_load_stackoverflow) *
EP0018063A1 (en) * 1979-02-12 1980-10-29 Diamond Shamrock Corporation Pyridazin (2H)-3-ones, process for their preparation and their use in antihypertensive agents

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5883090A (en) * 1995-10-09 1999-03-16 Merck Patent Gesellschaft Mit Beschrankter Haftung Endothelin receptor antagonists
WO2000050408A1 (fr) * 1999-02-26 2000-08-31 Kowa Co., Ltd. Derives de pyridazin-3-one et medicaments contenant ces derives
AU764393B2 (en) * 1999-02-26 2003-08-14 Kowa Co., Ltd. Pyridazin-3-one derivatives and medicines containing the same
US6680316B1 (en) 1999-02-26 2004-01-20 Kowa Co., Ltd. Pyridazin-3-one derivatives and medicines containing the same
US10899743B2 (en) 2015-08-05 2021-01-26 Bristol-Myers Squibb Company Substituted glycine derived FXIA inhibitors

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DK158082A (da) 1982-04-06
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ZA815411B (en) 1982-08-25
PT73487A (en) 1981-09-01
GR75327B (enrdf_load_stackoverflow) 1984-07-13
WO1982000402A1 (en) 1982-02-18
IL63514A0 (en) 1981-11-30
ES504577A0 (es) 1982-12-16
ZW19081A1 (en) 1982-03-03
JPS57501328A (enrdf_load_stackoverflow) 1982-07-29

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